Metallized monoazodyestuffs containing a dihalopyrimidyl group



United States Patent "i e 3,288,771

Patented Nov. 29, 1966 3 288 777 the group NH being bound to one of the positions 6 a and 7 and the whole metal complex compound bearing gES&%$ g at least two and at most four sulfonic acid groups; Jakob Benz, Oberwil, Basel-Land, and August Schweizer, g The 1:1 copper 1:1 mckd 1:2 chromlum or 1:2 Muttenz, BaseLLaud, Switzerland assignors to sandoz co at complex compounds of the monoazo dyestuffs of Ltd. (also known as Sandoz A.G.), Basel, Switzerland the formula No Drawing. Filed Mar. 4, 1963, Ser. No. 262,377 N Claims priority, application Switzerland, Nov. 29, 1957, l 53,195/57; July 27, 1961, 8,863/61; Dec. 18, 1962, OH OH I -3 i 14,832/62 N 0E 15 Claims. Cl. 260-146) 10 (HOaS)nAr1N=N a The present application is a continuation-in-part of our Hons T application Ser. No. 775,346, filed November 21, 1958 I I (abandoned since the filing of the present application), S (In) and relates to metalliferous azo dyestuffs bearing a reactive dihalopyrimidyl group. Especially, it concerns the 1:1 copper, 1:1 nickel, 1:2 chromium and 1:2 cobalt complex compounds of the monoazo dyestufi's of the formula wherein Ar is a naphthalene radical bearing OH in orthoposition to N=N,

hal is a halogen atom with an atomic number from 17 to 35 inclusive,

N one sis a hydrogen atom and the other sis SO H OH OH l 1 H and n is an integer from 1 to 2, inclusive,

| CH (Ho s nir-N=N nso n l the whole metal complex compound hearing at least three and at most six sulfonic acid groups;

(c) The 1:1 copper or 1:1 nickel complex compounds (I) of the monoazo dyestuffs of the formula OH C-N CH=CHONH fi- N CH (H0 S)nArzN=NO SOaH 603B 0 O=N l Thal CH; 8 (IV) wherein Ar is an aromatic radical selected from the benwherein Ar is aradical of the benzene series,

zene and naphthalene series bearing OH in orthohal is a halogen atom with an atomic number from 17 position to N=N, to 35, inclusive,

EOH is the radical of a coupling component selected andn is an integer from 1 to 2, inclusive;

from the hydroxy-naphthalene and the S-pyrazolone 40 (d) The 1:1 copper, 1:1 nickel, 1:2 chromium or 1:2 series, OH being in a position vicinal to N=N, cobalt complex compounds of the monoazo dyestuffs of hal is a halogen atom with an atomic number from 17 to the formula 35, inclusive, i.e., is chlorine or bromine, n is an integer from 1 to 2 inclusive, 011 p is an integer from 1 to 3, inclusive, C| H R *N=N E1(S 0 3H) -1 the whole metal complex compound bearing at least two and at most six sulfonic acid groups.

Among the metal complex compounds of the monoazo dyestuffs encompassed by the above Formula I the following groups are especially valuable:

(a) The 1:1 copper, 1:1 nickel, 1:2 chromium or 1:2 cobalt complex compounds of the monoazo dyestuffs of wherein E OH is the radical of a hydroxy-naphthalene the formula coupled in ortho-position to OH,

OH one R is SO H clan /N\ the second R is (HOaS)nArN=N 3 N CH N H0 8 Y6 \C/ C% \C Y l T NH- I I (5H (II) c lie! I a (v1) wherein AI is an aromatic radical selected from the benzene and naphthalene series bearing OH in orthoposition to N=N, hal being a halogen atom with an atomic number from 17 hal 1s a halogen atom with an atomic number from 17 to t 3 5, i l i 35 inclusive, and p is an integer from 1 to 3 inclusive, Y 1s a member selected from the group conslstmg of hydrogen and 40 K 70 the whole metal complex compound hearing at least two and n 1s an mteger from 1 to 2, inclusive, and at most four sulfonic acid groups;

(e) The 1:2 chromium or 1:2 cobalt complex compounds of the monoazo dyestuifs of the formula I OH R I (VII) wherein E OH is the radical of an enolized 5-pyrazolone coupled in a position vicinal to OH, one R is SO H, the second R is hal (VI) hal being a halogen atom with an atomic number from 17 to 35, inclusive,

and p is an integer from 1 to 3, inclusive,

the whole metal complex compound bearing at least two and at most six sulfonic acid groups.

A process for the production of the metal complex compounds of the monoazo dyestuffs of the Formula I consists in reacting 1 mole of a dyestuif of the formula OH OH i i NHg (HO S)nArN=NE(S0 H)ni i (VIII) in either order with 1 mole of a 2,4,6-trihalopyrimidine and with a metal-yielding agent, so that one halogen atom of the 2,4,6-trihalopyrimidine combines with one hydrogen atom of the amino group and the remaining dihalopyrimidyl radical becomes attached to the dyestuif radical through the NH bridge member, and that the metal- .yielding agent reacts with the ortho-orho'-dihydroxy-azo grouping to form the metal complex compound.

In the dyestuffs of the Formula VIII, the amino group, e.g., when it stands in orthoor in peri-position to a hydroxy group, reacts only diflicultly with the 2,4,6-trihalopyrimidine, perhaps because of the formation of a hydrogen bridge between the amino group and the vicinal hydroxy group; in these cases it is advisable to metallize first the dyestuff of the Formula VIII and, when the orthoortho'-dihydroxyazo group is closedby a metal atom, to carry out the condensation of the amino group with the 2,4,6-trihalopyrimidine; then the condensation proceeds smoothly and completely.

A modification of the procedure outlined above (a) consists in condensnig 1 mole of a diazo component of the formula 0H HzN1ir-X (s men (1x wherein n and Ar have the afore-cited meanings,

and X is a nitro group or an easily splittable acyl group,

e.g., the acetyl group, OH and X being in ortho-position to each other,

with at least 1 mole of 2,4,6-trihalopyrimidine, reducing the nitro group or splitting off the acyl group, diazotizing the amine, coupling the diazo compound with a coupling component of the hydroxynaphthalene or the 5-pyrazolone series which couples in ortho-position to the phenolic or enolic hvdroxy group and metallizing the obtained dyestuff, the reactions, especially the reduction of NO or the hydrolysis of NH- acyl, being carried out under such conditions, e.g., reduction with iron and dilute acetic acid solution at 90-95 (B champ method) or hydrolysis with 510% hydrochloric acid at 80-100, that the dihalopyrimidyl group is not damaged;

or (b) condensing 1 mole of a coupling component of the formula OH HNH2 3 )l -l wherein p and E have the above-cited meanings, and H is in ortho-position to OH, wtih at least 1 mole of 2,4,6-

trihalopyrimidine, coupling with the diazo compound of an amine of the formula OH (HO S)n--LrNHz (XI wherein n and Ar have the above-cited meanings, and metallizing the obtained dyestuff.

A second modification of the procedure outlined above consists in simultaneously oxidizing and coppering a dyestufi of the formula amn-1 (XII) wherein E, n and p have the above-cited meanings,

and when acyl is an easily splittable acyl group, splitting off this group under such conditions that the copper complex is not damaged, i.e., under alkaline conditions, e.g., in 4 to 8% sodium or potassium hydroxide solution at to C., and condensing with 2,4,6-trihalopyrimidine.

When, instead of the 1:1 copper complex compound, the 1:1 nickel, 1:2 chromium or 1:2 cobalt complex compound is desired, decoppering is eliected by treating with an aqueous solution of a strong acid, e.g., 540% hydrochloric acid or with a cold aqueous solution of sodium sulfide or sodium hydrogen sulfide, the treatment being so effected that the reactive dihalopyrimidyl group remains unaffected. When acyl is, e.g., an acetyl group, decoppering can be effected simultaneously with the hydrolysis, e.g., by means of 540% hydrochloric acid at 80100 C. Then the ortho-ortho'-dihydroxy azo dyestuif is precipitated in the acid medium and separated from the dissolved copper salts by filtration, whereas, when sodium sulfide or sodium hydrogen sulfide is used, copper sulfide is precipitated and the dyestuffs remain dissolved.

The radicals Ar and E in Formula I may be further substituted, e.g., by halogen atom (chlorine, bromine), nitro groups, lower alkyl groups (methyl, ethyl), acylamino groups (acetylamino, benzoylamino) or an optionally substituted sulfonic acid amide group. If E is a 5-pyrazolone radical the substituents other than the -OH group are bound to the l-aryl radical which can be phenyl, 1- or Z-naphthyl or stilbenyl.

The condensation with 2,4,6-trihalopyrimidine is conducted preferably in aqueous medium. The halide can be applied in concentrated form or dissolved in an organic solvent. Solvents specially suitable for halopyrimidines are acetone, benzene, chlorobenzene and toluene.

The temperature of reaction depends on the reactivity of the individual starting materials and varies from 20 to 100 (1., preferably from 40 to 80 C. If temperatures higher than about 40 C. are necessary, it is advisable in view of the volatility of 2,4,6-trihalopyrimidines in watersteam to work with vessels fitted with reflux condensers.

The reaction is carried out in a weakly alkaline, neutral or weakly acid medium, but preferably in the pH region of 8.0 to 4.0. To neutralize the hydrogen halide so formed an acid-binding agent, e.g., sodium acetate, is added to the reaction solution at the start of the operation, or, if preferred, small portions of sodium or potassium carbonate or sodium or potassium bicarbonate in solid poWdered form or as a concentrated aqueous solution are added in the course of the reaction. Aqueous solutions of sodium or potassium hydroxide are other suitable neutralizing agents. The addition of small amounts of a wetting or emulsifying agent to the reaction mixture can accelerate the rate of reaction.

By using at least 1 mole of 2,4,6-trihalopyrimidine for the amino group to be reacted, the condensation is so controlled that only one halogen atom of the 2,4,6-trihalopyrimidine reacts with an exchangeable hydrogen atom of the amino group. Hitherto it has not been possible to determine which of the halogen atoms participates in the reaction or whether it is equally probable that either one of the two isomeric forms will be formed.

The diazotization of the amines is carried out by the direct or the indirect method at temperatures of, e.g., to 15 C. The coupling reaction is conducted in a weakly acid, neutral or alkaline medium, preferably at pH 6 to 12, and at low temperatures, e.g., to 10 C., if necessary in presence of organic bases such as pyridine or a mixture of pyridine bases.

The ortho-ortho-dihydroxy azo dyestuffs are advantageously converted into the 1:1 copper or 1:1 nickel complex dyestuffs in aqueous, weakly acid (e.g., acetic acid) to weakly alkaline solution at temperatures of 4080 C. and in presence of an aqueous solution of an alkali metal salt of a low molecular aliphatic monocarboxylic acid. The copperor nickel-yielding agent is employed in such amounts that 1 atom of metal acts upon 1 molecule of dyestufl.

The conversion of the ortho-ort-ho'-dihydroxyazo dyestuffs into their 1:2 chromium or 1:2 cobalt complex compounds is carried out to best advantage in aqueous solution or in organic medium, for example formamide, or in the concentrated aqueous solution of an alkali metal salt or a low molecular aliphatic monocarboxylic acid. It is advantageous to proportion the reactants so that an amount of the metal-yielding agent containing less than two but at least one atom of metal acts upon two molecules of the monoazo dyestuff.

Suitable chromium compounds are, e.g., chromic fluoride, chromic sulfate, chromic formate, chroniic acetate, potassium chromic sulfate or ammonium chromic sulfate. The chromates also, e.g., sodium or potassium chromate or bichromate, are eminently suitable for metallizing the monoazo dyestuffs. In the latter case it is advisable to work in a strongly caustic alkaline medium to which reducing substances may be added if necessary, and to carry out the metallization before the introduction of the dihalopyrimidyl group which is sensitive to strong alkalies and could be damaged.

Examples of suitable cobalt compounds are cobaltous formate, cobaltous acetate and cobaltous sulfate. When metallizing is conducted in the concentrated aqueous solution of an alkali-metal salt of a low molecular aliphatic monocarboxylic acid, water-insoluble metal compounds, e.g., cobalt hydroxide or cobalt carbonate, can also be employed. It is particularly advantageous to carry out metallizing in an aqueous or alkaline medium to which the metal compounds are added in presence of compounds which maintain the metal dissolved in complex combination in caustic alkaline medium, e.g., tartaric acid, citric acid or lactic acid. Here also it is advisable to carry out the .metallization before the introduction of the dihalopyrimidyl group.

The chromiumor cobalt-containing azo dyestuffs which are obtained are homogeneou metal complex compounds in which essentially one metal atom is combined with two molecules of the monoazo compound.

The metal complex compound-s are so called 1:2 complexes in which one molecule of the monoazo compound is combined with about 0.3 to 0.7 atom of metal.

The organic metallizing solution can be run into brine if desired and the metal complex compound is then precipitated from the aqueous medium by the addition of salt, filtered off, washed if necessary and dried.

The new metal-containing reactive dyestuffs are suitable for the dyeing of leather; the dyeing, padding and printing of fibers of animal origin, e.g. wool and silk; synthetic polyamide fibers, e.g. nylon; cellulosic fibers, e.g. cotton, linen; regenerated cellulosic fibers, e.g. viscose filament yarn, viscose staple fibers and cuprammonium rayon; and mixture and/or other articles of these fibers. The optimum conditions of application vary with the nature of the fiber and the dyestuffs used.

The copperor nickel-containing monoazo dyestuffs which bear 3 or more water-solubilizing groups, e.g., carboxylic or preferably sulfonic acid groupsother groups such as alkylsulfonyl or optionally substituted sulfonic acid amide groups have a limited importance because their introduction into the molecule is rather difficult-the chromiumor cobalt-containing dyestuffs which bear 2 or more water-solublizing groups for each molecule of the Formula I possess good solubility in water, good stability in printing pastes and padding liquors, good compatibility to salts and hard water, good reactivity with vegetable fibers, animal and synthetic polyamide fibers; they are insensitive to heavy metals such as copper, iron and chromium and reserve acetate, triacetate, polyester, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate and polyalkylene fibers. In general, i.e., with the exception of the copper and nickel complex compounds of the monoazo dyestuffs of the Formula 1V and of certain monoazo dyestuffs of the Formula II derived from 2-arnino-5-hydroxynaphthalene-lsul-fonic acid, they are rather slightly substantive or not substantive at all, so that the unfixed dyestuff portion can easily be removed from the dyeings and prints on cellulosic fibers.

The copperor nickel-containing monoazo dyestuffs which bear 2 to 3 water-solubilizing groups and also the copper and nickel complex compounds of the monoazo dyestuffs of the Formula IV and of certain monoazo dyestuffs of the Formula II derived from Z-amino-S-hydroxynaphthalene-7-sulfonic acid, which contain 3 or 4 Watersolu'bilizing groups, preferably sulfonic acid groups are especially suitable for the so-called exhaustion dyeing of cellulosic fibers, whereas for the .chromiumor cobaltcontaining dye stuffs which bear 1 to 2 Water-solubilizing groups for each molecule of the Formula I the principal application field is the normal acid dyeing of wool, silk and synthetic polamide fibers.

Animal fibers and synthetic polyamide fibers are dyed, printed or fixed preferably in acid, neutral or weakly alkaline medium, e.g., in presence of acetic, formic or sulfuric acid, ammonium sulfate, sodium metaphosphate, etc. Dyeing can be carried out in a neutral to acetic acid medium in presence of levelling agents, e.g., polyoxethylated fatty amines or mixtures of these and alkylpolyglycol ethers, and the bath adjusted to a neutral or weakly alkaline reaction at the end of dyeing by the addition of small amounts of an agent of alkaline reaction, e.g., ammonia, sodium bicarbonate, sodium carbonate, etc., or of compounds which react alkaline onheating, e.g., hexamethylene tetralmine, urea. The goods are then well rinsed and if necessary soured with a little acetic acid.

The dyeing, padding and printing or fixing of the dyestuffs on cellulosic fibers is carried out in alkaline medium, e.g., in presence of sodium bicarbonate, sodium carbonate, sodium hydroxide solution, potassium hydroxide solution, sodium rnetasilicate, sodium bonate, trisodium phosphate, ammonia etc. To prevent reduction effects during dyeing, padding or printing it is often advantageous to use a mild oxidizing agent, e.g., sodium 1-nitrobenzene-3-sulfonate. The fixation of the dyestuffs on cellulose fibers is carried out as a rule with heating, e.g., by steaming, by thermofixing, by treatment in a hot aqueous alkaline solution containing neutral salts or by conditioning in a hot moist atmosphere. The dyestuffs which are well soluble in a solution containing neutral salts, e.g., calcined sodium sulfate in amounts of about 20 to about 150 grams per liter and a strong alkali, e.g., sodium metasilicate, triparts of crystallized copper sulfate is added at 7O -8O in such an amount that the monoazo dye is entirely converted into the copper complex compound. The metallized dye is precipitated by the addition of sodium chloride,

sodium phosphate, sodium or potassium hydroxide and in 5 filtered off and washed with a sodium chloride solution. this solution possess a sufiicient substantivity to draw onto The moist copper complex dye is dissolved in 500* parts cellulosic fibers can also be dyed and fixed by irnpregnaof water at 70 and the solution is adjusted to the pH-value tion and storage at lower temperatures, e.g., 20 to 40 of 5. After the addition of 9 parts of 2,4,6-triehloro- C. (Pad Batch Dyeing Process). pyrimidine the reaction mixture is vigorously stirred at The addition of certain quaternisable amines such as 10 65-700 With reiiilX, a 'diiuifi Sodium Carbonaifi Solution trimethylam-ine, triethylenedialmi-ne, asymmetric dimethylbeing added to P a Constant Weakly acid Teaciiim h d i N j iidi f bl i gtoichio- (pH-value 46) The reaction product is then precipitated metric amounts, accelerates the fixation of the dyestuii With Sodium Chloride A r filtration, the press cake on the fiber, so that the fixation temperature can be lowiS dried in M0110 at Tile ground dyesiuif is a eyed d/o h fi ti ti h t dark powder which dissolves in water with a blue-red The dyein-gs and prints on lcellulosic fibers are notable Colorationfor their outstanding wet fastness properties which are due 1 P of the Pi Y Obtained as to the formation of a chemical linka b t th d above is dissolved in 3000 parts of softened water at 60. stuif molecule and the cellulose molecule. Often the 100 parts of wetted viscose raY are entered in this y total amount of applied dyestuff does not take part in the bathreaction, in which case the unfixed dyestuff is removed The iemliel'atufe is increased in 15 millilifls and by suitable treatment such as rinsing and/ or soaping, if dyeing continued for 45 minutes at the same temperature necessary at higher tempepatzure, POT this purpcse gyn With constant agitation Of the goods. During this time thetic detergents, e.g. alkylarylsulf'onates, sodium lauryl 200 Paris calcined Sodium sulfate are added in 3 P sulfate, sodium lauryl polyglycol ether sulfate, optionally tiQIlS- At this Point 3 Concentrated Soiiutioll (if 5 Paris apboxymethylated alky'lpglyglyool etheps monoc and Of SOdlUJIIl l-nitro=benZene-3asulfonate added, followed alkylphenylpolyglycol ethers, can be used. by parts of trisodium phosphate. The material is then The dyeings and prints on celluliosic fijbers possess good W01 ked about in the alkaline bath f0! 1 hour at 90- The fastness to light, washing, water, sea water, cross dyeing, dyeing thus obtained is rinsed in cold and warm water, perspiration, pressing, rubbing, alkali, e.g., soda ash, soda 30 Soaped at the boil for 20 minutes, Well rinsed and dried. boiling, acids, e.g., acetic acid, tartaric acid, citric acid and A bluish red y of good light and Wet fastness its fruit juices, vulcanizing, chlorine, e.g., chlorinated swim- P ming pool water, bleaching (peroxides), gas fumes and The following Table 1 contains 2611111161 :rnetalliferous dry cleaning (organic solvents). In addition they are 810 dye'siiliis p p in a manner similar 10 that stable to resin finishing and to acid and alkaline hydrolytic Scribed in Example are 111 PP 111 nickel, influences. The dyeings and prints on wool and synth ti 1:2 chromium or 1:2 cobalt complex compounds of the polyamide fibers possess a good fastness to light and dy stuffs f he formula excellent fastness properties to Washing, water, sea water, OH milling, perspiration, rubbing, pressing, sublimation and 011 N "I dry cleaning. 40 (HQBS)B AI N=N Ha1 In the following examples the parts and percentages are 2 i by Weight and the temperatures in degrees centigrade. E033 Example 1 9.5 parts of 1-amino-2-hydroxybenzene-5-sulfonic acid Haul are suspended in 200 parts of Water and 2 parts of 30% and are cilamcifii'iled by diam component hydrochloric acid are added to the suspension. Diazo- 0H tization is carried out at 1015 by adding a concentrated 1 aqueous solution of 3.5 parts of sodium nitrite and stirring (H.03S) Ar NH2 the suspension until all is dissolved. The solution of the (column the coupling Component diazo compound is run into a solution cooled to 510 of 12 parts of Z-auninod-hydroxynaphthalenefl-sulfonic OH acid and 20 parts of sodium carbonate in 200 parts of water. When coupling is completed the solution is heated to 50-60", then the formed monoazo dye is precipitated by the addition of sodium chloride, filtered off and washed H03 with a solution of sodium chloride.

The dye paste is dissolved in 500 parts of water at p in the Position i0 2 (C n H), th hal g n 70 and the pH-value is adjusted to 5 by the addition of (Column III), the metal employed for the metal complex a little 40% acetic acid solution. After the addition of formation (Oolurnn IV) and the shade of the dyeing on 15 parts of crystallized sodium acetate :1 solution of 12.5 cotton (Column V).

TABLE 1 fifi (I) (II) (III) IV v 2 1-amino-2-hydroxybenzene-5-sulionic acid. 1-hydr0xy-7-aminonaphthalene-3-sulfonic C1 Cu Bluish red.

1-arnino 2-hydroxy-5-1nethylbenzene-il-liizdibxy-fi-aminonaphthalene-3asulionic Do.

sulfonic acid. acid. l-aggiilno-2-hydroxybenzene-3,S-disulfonie do Do.

do I:III 1Q .II:I IIIg II:IIIIIIIIIIII: 1 38: do l-hydlroxy-7-aminonaphthalene-3-suli'onic D0. l-amino-Q-hydroxy-El-carboxybenzene-E- 1ig moxy-ti-aminonaphthalene-Eisulionic Do.

sultonic aci acid. l-an ino-zhydroxybenzene-S-sulfonic 1hydroxy-6'aminonaphtha1ene-3,5-disul- Do.

acid. tonic acid.

TABLE 1C0ntinued ag (1) (11 (III) (Iv) (v) 10 l-amino-2-liydroxynaphthalene-i-sulfonic 1-hyd;0xy-6-aminonaphthalcne-3-sulionic Reddish blue.

acid. aci 11 l-amino-Z-hydroxynaphthalene-4,6-disul- .do Do.

ionic acid. 12 do d Br Cu Do. 13 l-amino-2-hydroxy-3-chl0robenzene-5- do Cl Cr Violet.

sul ionic acid. i yg 1-liydroxy-6 aminonaphthalene-3-sulfonic 14 1 g g g a 3 0110 b n e 5 ac Reddish navy blue.

g ga' g l m e 2 2-hydroxy-S-acetyl-aminonaphthalene 1-amino 2-hydroxy-3chlorobenzene-5- 1-hydr0xy-G-aminonaphthalene-3-sulfonic sulfonic acid. acid. Do. 1-amino-2-hydr0xybenzene-5-sulfonicacid- Z-hydroxy-S-aminonaphthalene l-amino-Q-hydroxy-5-chlorobenzene-3- 1-hydroxy-7-aminonaphthalene-3-sulionic Blue-violet.

sulfonic acid. acid. l-amino-2-hydroxy-3-chlorobenzene-5- 1-hydrcxy-fi-aminonaphthalene-3-sulf0nic Violet.

sulfonic acid. acid. 1-amino-2-hydroxybenzene-S-sulfonic acid do Violettish brown. .do .do Do.

Example 20 N h l parts of 1-diazo-2-hydroxynaphth-alene-4-sulfon1c a acid are added to a solution of 32 parts of 1-amino-8- OH NH OH I N CH hydroxynaphthalene-3,6-disulfonic acid, parts of sodium carbonate and 30 parts of pyridine in 300 parts of 2 (HO8S)e AY-N=N water. The reaction mixture is stirred for several hours hal at room temperature until coupling is complete. It is 1101s S2 then acidified with hydrochloric acid and sodium chloride added causing precipitation of the blue m-onoazo dye, S1 which is filtered off and Washed with a sodium chloride 30 and are GhaTHCIETIZed y thfl diazo component solution acidified with hydrochloric acid. OH

The moist dye is dissolved in 400 parts of water at 70 and the solution adjusted to a pH-value of 4 with sodium hydroxide solution. 27 parts of crystallized sodium acetate are added. At 70-80 a concentrated aqueous solution of 25 parts of crystallized copper sulfat is run in in suflicient quantity to bring about complete conversion 5 and IV), the :metal used for the metal complex formation (Column V) and the shade of the dyeing on cotton (Column VI) TABLE 2 Example (I) (II) (III) (IV) (V) (VI) 21 l-hydroxy-2-aminonaphthalene- H SO;H Cl Cu Violet.

4-sulf0nic acid. 2 d0 H SO H Cl Ni Red-violet. 23 l-hydroxy-Q-aminoanaphtha- H SO H Cl Cu Violet.

lene-4,6disulf0nic acid. 24 do H SO H Br Do. 25 l-hydroxy2-aminonaphthalene- H SO H Cl D0.

4,8-disulfonic acid. 26 l-amino-2-hydroxynaphthalcne- SOaH H Cl Do.

4-sulfonic acid. 27 -do H SO3H C1 Dark green.

H D0. D0.

Gray-black.

of the monoazo dye into its copper complex compound. When this is accomplished 15 parts of 2,4,6-trichloropyrimidine are added and the reaction mixture stirred in a closed vessel at 70-80", the pH-value being maintained between 4 and 6 by the gradual addition of 20% sodium carbonate solution. When the reaction has run its course the product is precipitated with sodium chloride and cooling, then filtered off and washed with dilute sodium chloride solution. On drying and grinding it is obtained as a brown-black powder which dissolves in water with a violet coloration.

In the following Table 2 are listed nietalliferous azo dyestuffs obtained in a manner similar to that described in Example 20; they are the 1:1 copper, 1:1 nickel, 1:2 chromium or 1:2 cobalt complex compounds of the dyestufis of the formula Example 31 27 parts of l-amino-Z-hydroxybenzene-3,S-disulfonic acid are dissolved in 150 parts of water and diazotized at 15 with 7 parts of sodium nitrite.

47.5 parts of 1-[4"-aminostilbenyl-(4)]-3-methyl-5- pyrazolone-2',2"-sulfonic acid are dissolved in 300 parts of water with the addition of sodium hydroxide solution at pH 7-8. On cooling to 10 20 parts of sodium bicarbonate are added to the solution. pound prepared as given above is allowed to flow slowly into this mixture with good stirring. It couples to form a yellow monoazo dye.-

On completion of the coupling reaction the solution is adjusted to pH 4.5 with hydrochloric acid and heated to 27 parts of crystallized sodium acetate are added, then an aqueous solution of 25 parts of crystal- The diazo com' 1 l 1 2 lized copper sulfate is run in. The reaction mixture is The dye paste is dissolved in 500 parts of water at 70 stirred for a further hour at 80. The copper complex and the solution adjusted to the pH-value of 5. Then 27 compound of the monoazo dye thus formed is precipitated parts of crystallized sodium acetate are added, followed by theaddition of sodium chloride and cooling to 30, by a solution of 25 parts of crystallized copper sulfate at filtered off, and purified by redissolving and reprecipita- 5 7080 in an amount suflicient to completely convert the ti from the aqueous solution, aminoazo dye into the copper complex compound. The The purified copper complex compound is dissolved in resulting metallized aminomon-azo dye is completely 1000 Parts f water t 80 15 parts of 2,4,6-trih1or precipitated by the addition of sodium chloride, filtered pyrimidine are added. The reaction mass is stirred in a OE and Washed with aqueous sodium chloride solution. closed vessel at 8090, its pH value being maintained The moist dye paste is dissolved in 1000 parts of water between 6 and 7 by adding 20% sodium carbonate soat 80. 16 parts of 2,4,6-trichloropyrimidine are added lution. When the reaction is finished the product is preand e mixture stirred in the closed vessel at 80-90". cipitated at 50 with sodium chloride, filtered off, washed T e pH-value is maintained between 5 and 6 by adding with dilute soduim chloride solution, dried and ground. a 20% sodium carbonate solution. When the reaction A brown power is obtained which dissolves in water to is finished the product is precipitated by adding sodium .give yellow brQWn 1 i chloride and cooling, and then filtered off, washed with Mercerized cotton sateen fabric is dyed with this dye aqueous Sodium Chloride Solution, dried and ground- It by the method given in Example 1 except that the trisois obtained as a dark brown power which dissolves in dium phosphate there used is replaced by an equal Water a blue-red coloration. amount of sodium or potassium carbonate. A yellow- A mercerized cotton fabric is padded with a warm, brown dyeing fast to light and wet treatments is obtained. neutral Solution of 3 parts of the above copper complex The following Table 3 contains further metalliferous dye and 1 part of sodium 3-nitrobenzene-l-sulfonate in azo dyestuffs produced in a manner similar to that de- 100 parts of Water, and squeezed to retain about 85% scribed in Example 31; they are the 1:1 copper or 1:1 of its Weight of the solution. After drying, it is entered nickel complex compounds of dyestuffs of the formula in a bath of 250 Parts Of anhydrous Sodium S l ate and (HO S),.Ar N=NC I soan B038 0 C=N l 1 hal CH and are characterized by the diazo component parts of sodium carbonate per 1000 parts treated with on agitation for about minutes at 80-90 to fix the dyeing. The liquor ratio of this bath may be 1:10 to 1:50. On fixation, the dyed fabric is rinsed well and dried. The (Column I), the halogen (Column 11), the metal used bluish red dyeing obtained has excellent light and wet for the metal complex formation (Column III) and the fastness. shade of the dyeing on cotton (Column IV). 40 In the following Table 4 are disclosed further metal- TABLE 3;

Ex. No. (I)

32 l-amgio-2-hydroxybenzene-5-sulionic C1 Cu Yellow-brown.

2.81 3'4 do Cl Do. 34 l-amino-Z-hydroxybenzene-b,5-disul- Br-" Do.

ionic acid. 35 o C1 Do. 36 1-amino-Zhydroxy-E-carboxy-benzene- Cl Do.

fi-sulfonic acid. 37 do 01 Do, 38 l-amino-Z-hydroxy-Schlorobenzene-d C1 D0.

sulfonic acid. 39 l-amino-Z-hydroxy-5-ohlorobenzene-3- Br Do.

sulionic acid. 40 1-amino-2-hydroxy-5-nitrobenzene-3- Cl D0.

sulfonic acid. 41 l-amino-Z-hydroxy-B-nitrobenzene-5- Cl Do.

sulfonic acid.

Example 42 liferous azo dyestuffs produced in a manner similar to that described in Example 42; they are the 1:1 copper, 1:1 nickel 1:2 chromium or 1:2 cobalt com lex comacetylammobenzene-S-sulfon1c acid in 100 parts of water, P

100 parts of ice and 5 parts of 20% hydrochloric acid is Pounds of h dyestuffs of the formula diazotized at 3-5 with 29.5 parts of 4 normal sodium 011 nitrite solution. The diazo compound is run slowly into A suspension of 24.6 parts of 1-amino2-hydroxy-3- 1 a solution of 24 parts of 2-hydroxynaphthalene-6-sulfonic 1 N=NE1( 3 0111 acid and 25 parts of sodium carbonate in 350 parts of 'water. On completion of coupling the resulting acetylaminomonoazo dye is precipitated with sodium chloride,

filtered off and washed with aqueous sodium chloride a ol ti and are characterized by the symbols R and R (Columns The moist filter cake is entered into 700 parts of 5% I and II), the coupling component hydrochloric acid. The mixture is brought to the boil 0H and boiled for 1-2 hours until the acetyl-group is split I 0E. The aminomonoazo dye is precipitated by adding HEI (SO3H)"" sodium chloride with cooling, filtered off and washed coupled in orth-o-position to OH (Column III), the with aqueous sodium chloride solution. metal used in the metal complex formation (Column IV) and th'eshade of the dyeing on cotton (Column V); in washed with aqueous sodium chloride solution. After Columns I or II dichloropyr. and dibromopyr. represent drying and grinding a dark brown powder is obtained which dissolves in water with a brown coloration.

N I N '1 A mercerized cotton sateen fabric is printed with a 5 printing paste of the following composition:

I iH and I l L-H 20 parts of the above dye 100 parts of. urea L 405 parts of water C1 450 parts of a 3% sodium alginate thickening TABLE 4 Dichloropyr -SO;H l-hyddroxynaphthalenet-sulfonic Bluish-red.

acr Dichloropyr SO H Lhydroxynaphthalene-B,6-disul- Do.

tonic acid. Dichloropyr... -SO H Red. Dichloropyr SO;H 1-hydroxynaphthalene4,fi-disul- Bluish red.

tonic acld. Dibromopynt SO H do Do. -SO;H Dichloropyr do Cu Do. SO;H Dichloropyr 1-hydroxynaphthalene-3,fi-disul- Cu D0.

tonic acid. SO H Dichloropyr 2-hydroxynaphthalene-3,6-disu1- Ni Red.

ionic acid. SO3H Dichloropyr- 2-hy%roxynaphthalene-6-sulionic Cr Gray-violet.

2101 SO H Dichloropyr... 2-hy i(l1roxynaphthalene-4-sulfonic C0 Bluish red.

acl Dichloropyr-.- SO3H -do Cr Gray-violet. Dichloropyr... -SO H 1-hydlroxynaphthalene-i-sulfonic Cr Do.

an Dibromopyr Do. Dibromopyr B ordeaux. Dichloropyr do o.

Dichloropyr... l-hydroxy-6-phenylamin0-naph- Reddish thalene-3sulfonic acid. gray.

Dichloropyr... -SO H l-hydroxy-tlphenylarnino-naph- Cu Bordeaux.

thalene-3, 3-disul[onic acid. Dichl0ropyr SO H 2-hydroxynaphthalene Co Bluishred. Dichloropyr.-- SO H Z-hydroxy-8-acctylaminonaph- Cr Gray.

thalene.

Example 62 i 10 parts of 3-nitrobenzene-1-sulfonate A suspension of 24.6 parts of l-amino-2-hydroxy-3- parts of'c'alcmed Sodmmcarbonate acetylaminobenzene-S-sulfonic acid in 100 parts of water, 100 parts of ice and 5 parts of hydrochloric acid 45 L000 parts total is diazotized at 3-5 with 29.5 parts of 4 normal sodium The print i dried, Steamed f 1 minutes at 0 404 nitrite solution. The diazo compound is run slowly into and rinsed well in cold and in Warm Watm It is then a solution of 35 parts of 1-(2 5'-dichlorophenyl)-3- soaped for 10 minutes at the boil with a 0.3% soap solu- 'Q Y -PY Q acld and Parts tion in distilled water, rinsed again and dried. A brown sodlum carbonate 9 Parts of f O11 completlofl print with excellent wet fastness properties is obtained. of Q P Tesultmg acetylamlniomonoazo y 15 The following Table 5 contains further metalliferous precipitated with sodium chloride, filtered oif and washed azo d t flproduced in a manner i i to that d With aqueous Sodium chloride Solutionscribed in Example 62; they are the 1:2 chromium or 1:2

h i k is into Parts of 5 cobalt complex compounds of. the dystufis of the formula hydrochloric acid. The m1xture is brought to the 13011 and boiled for 1-2 hours until the acetyl group is split OH oif. The aminomonoazo dye is precipitated by adding CN-ary1(SO H),- sodium chloride with cooling, filtered oil and washed R1 with aqueous sodium chloride solution.

The dye paste is dissolved in 500 parts of water at ([3=N 6070 and the solution adjusted to the pH 56. A CH3 concentrated aqueous solution of 12 parts of crystallized i cobalt sulfate (CoSO -7H O) is run in at an even rate inv sufficient quantity to Completely transform the and are characterized by the symbols R and R (Columns aminoazo dye into the 1:2 metal complex compound. I and the Tadlcal 'aryl 3 1 (Column III), At the Same time pH va1ue is maintained between the metal used for the metal complex formation (Column 5 and 6 by the addition of 20% sodium carbonate soluand the shade of the dyeing on cotton (column V); tion in Columns I or II dichloropyr. and dibromopyr. repre- When formation of the metal complex is complete, Sent 14 .parts of 2,4,6-trichloropyrimidine are added and the N I N I reaction mass stirred in the closed vessel for several Cl hours at 80-90". The pH-value is held at 5-6 during I II and [I this time by the addition of 20% sodium carbonate solugo tion. Cn completion of the reaction the dye is precip- C itated with sodium chloride and cooling, filtered oil and 17 18 Example 62 Example 68 r r N 6 1% 5 HC N HN i J HN v 01 H0 s-Q J N 00 cm-o-o f H+ I /00- CH3OC\ n Q NIII v v v c1 03Hv J J I Having thus disclosed the invention what we claim is: 80313 J2 i 1. A metal-complex dyestufl? selected from the group consisting of Y 1 i l, Example 63 5 (HO3S)n-ArN=N 7 Y tNH-Z 1103s 6 N 1 v H (H sS)n1|ir'O Hogs N Me:

L 3 0- OCHFCHGNEPZ i 6 SO3H J2 l R 19 20 and 3. The metal-containing dyestuff of the formula HO 5 N=N N i Q 5 3 oi N HO s NH ii- ILL Me: EH 3 N G H I 3 )v1 T 03H G Cl wherein Ar is an aromatic radical selected from the benzene and The metal-containing dyestuif of the formula naphthalene series bearing O- in ortho-position to A N:N O1Y1 O Ar is a naphthalene radical bearing --O in ortho- H S i position to N=N, O3 l Ar is a radical of the benzene series bearing --0- in H o oortho-position to N=N, 035 1; @5 E-O is the radical of a coupling component bearing 0 H -O- in a position vicinal to N=N and selected a C from the group consisting of the hydroxynaphtha-lene 01 and the 'S-pyrazolone series (in the enolized form), Y is a member selected from the group consisting of The metal'contammg dyast'ufi of the formula hydrogen and SO H, N one X is a hydrogen atom, l 01 the other x is 40m, 0 if one R is -SO H, 5 E N othe other R is -NH Z, HO3S Me; is a metal atom selected from the group consisting I of copper and nickel, H03S SO33 Me is a metal atom selected from the group consisting of chromium andv cobalt, n is an integer from 1 m2, inclusive, 6. The metal-contaimng dyest uff of the formula p is an integer from 1 to 3 inclusive, N and Z is the radical 35 [1 H i tH o o i H 110 s N=N o 0-H ('11 o h] 40 Hots sour h al a so H hal being a halogen atom with an atomic number from 3 17 to 35, inclusive. 7. The metal-containing dyes-tuif of the formula N 1 0ou-0\ 01 E OH=CH NH ll CH n0 N=NC l S0311 S0311 C C=N (E 8. The metal-containing dyestuff of the formula N 1 0--Cu-O c1 o- CH=CH NH 1 1| I INC i SOaH SOaH \C C=N l 1 Cl CH SO H 2. The metal-containing dyestuff of the formula 9. The metal-containing dyes-tufi oi the formula I 1'N N C1 F /N\ Q 0 Cl -o o i i o II I HN N=N Hogs -NH-- L 1 H H-C\ N c 03H 0 I 1 SOQH SOaH 

1. A METAL-COMPLEX DYESTUFF SELECTED FROM THE GROUP CONSISTING OF 